CN112708044A - Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN112708044A CN112708044A CN201911339722.9A CN201911339722A CN112708044A CN 112708044 A CN112708044 A CN 112708044A CN 201911339722 A CN201911339722 A CN 201911339722A CN 112708044 A CN112708044 A CN 112708044A
- Authority
- CN
- China
- Prior art keywords
- solution
- type super
- ether
- mud type
- polycarboxylate superplasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention relates to the technical field of concrete water reducing agents, in particular to an ether anti-mud type super-early-strength polycarboxylate water reducing agent and a preparation method thereof, wherein the ether anti-mud type super-early-strength polycarboxylate water reducing agent comprises the following preparation raw materials: methyl allyl polyoxyethylene ether, methoxypolyethylene glycol-acrylamide, allyl trimethyl ammonium chloride, unsaturated carboxylic acid, allyl amine, acrylamide, an oxidizing agent, a reducing agent, a chain transfer agent and methanol. The ether anti-mud type super early strength polycarboxylate superplasticizer provided by the invention increases the density of short side chain early strength groups on the basis of keeping the length of a main chain to be proper, and introduces methoxy polyethylene glycol-acrylamide (MPEG-ACA) with the molecular weight of 3000-5000-.
Description
Technical Field
The invention relates to the technical field of concrete water reducing agents, in particular to an ether anti-mud type super-early-strength polycarboxylate water reducing agent and a preparation method thereof.
Background
The polycarboxylate superplasticizer has the characteristics of high water reducing rate, high slump retention, low alkali, environmental protection and the like, and is widely applied to concrete engineering. However, the early strength development of the common polycarboxylic acid water reducing agent is slow, and particularly under the low-temperature condition, the use of the common polycarboxylic acid water reducing agent in winter construction and cold environment is limited, so that the early hydration of cement is promoted, and the development of the early strength polycarboxylic acid water reducing agent has obvious technical and economic benefits.
Regarding the super early strength type polycarboxylate water reducing agent, patent CN106749983A discloses a low density long side chain water reducing agent, which greatly improves the early strength of concrete by introducing long side chains into the main chain, reducing the long side chain density and introducing early strength groups into the water reducing agent molecules. Patent CN108192039A adopts polyether monomer with ultrahigh molecular weight as active macromonomer, so that molecular chain forms a structure with long side chain and short main chain, and introduces self-made small monomer of unsaturated alcohol amine ester and small monomer with early strength function such as dimethylaminoethyl methacrylate and triacrylate containing N group, and then the solution is polymerized at room temperature. However, no indication was found about the resistance to mud. The patent CN105199032A discloses a cation super early strength polycarboxylate superplasticizer, which is synthesized by taking various active macromonomers as raw materials and introducing cations into molecules, thereby reducing the adsorption of soil to an additive, accelerating the hydration of cement and having the super early strength function.
The polycarboxylic acid water reducing agent is widely applied to concrete engineering, and simultaneously, some obvious defects are exposed, particularly, the performance of the polycarboxylic acid water reducing agent is greatly influenced by soil contained in sand, so that the concrete has poor fluidity and great slump loss. In recent years, with the exhaustion of natural sand, machine-made sand or natural sand with poor quality is replaced, and the mud content of various aggregates is not reduced, so that the performance of the polycarboxylic acid water reducing agent is greatly influenced, the concrete fluidity is poor, and the slump loss is large.
At present, there are a few reports on the anti-mud agent. Patent CN102617811A proposes a method for preparing an amphoteric vinyl polymer concrete anti-mud agent. The preparation method comprises the steps of carrying out esterification reaction on methacrylic acid and polyethylene glycol monomethyl ether to prepare polyethylene glycol monomethyl ether methacrylate, and then carrying out free radical initiated polymerization on the polyethylene glycol monomethyl ether methacrylate, the acrylic monomer, the vinyl cationic monomer and the vinyl sulfonate monomer to prepare the polyethylene glycol monomethyl ether acrylate. Patent CN102775088A proposes a mud-resistant concrete water reducing agent and a preparation method thereof, wherein a quaternary ammonium salt type mud stabilizer, inorganic sylvite, an organic phosphorus scale inhibitor and a polycarboxylic acid water reducing agent are compounded for use.
Therefore, it is necessary to provide the polycarboxylate superplasticizer with the mud-blocking performance on the basis of having long side chains.
Disclosure of Invention
In order to solve the problem of poor mud resistance of the existing long-side-chain polycarboxylate superplasticizer in the background art, the invention provides an ether mud-resistant type super-early-strength polycarboxylate superplasticizer which has the following structural formula:
wherein a is 1 to 33, b is 1 to 555, c is 1 to 140, d is 0 to 140, e is 1 to 110, f is 0 to 37, m is 65 to 110, n is 89, and R is H or CH3。
The invention provides an ether anti-mud type super-early-strength polycarboxylate superplasticizer which comprises the following preparation raw materials: methyl allyl polyoxyethylene ether, methoxypolyethylene glycol-acrylamide, allyl trimethyl ammonium chloride, unsaturated carboxylic acid, allyl amine, acrylamide, an oxidizing agent, a reducing agent, a chain transfer agent and methanol.
On the basis of the scheme, the method further comprises the following preparation raw materials in parts by weight:
on the basis of the scheme, the molecular weight of the methoxypolyethylene glycol-acrylamide is 3000-5000, and the molecular weight of the methallyl polyoxyethylene ether is 4000.
On the basis of the scheme, further, the unsaturated carboxylic acid is one or a mixture of two of acrylic acid and methacrylic acid.
On the basis of the scheme, further, the oxidizing agent is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
On the basis of the scheme, further, the reducing agent is one or more of disodium hydrogen phosphite, potassium thiosulfate and ammonium formate.
On the basis of the scheme, the chain transfer agent is one or two of thiomalic acid and mercaptopropionic acid.
The invention also provides a preparation method of the ether anti-mud type super early strength polycarboxylate superplasticizer, which comprises the following preparation steps:
dissolving allyl amine in methanol, adjusting the temperature to 5-10 ℃, dropwise adding acrylamide and stirring under a protective atmosphere, preferably nitrogen, preferably electromagnetically stirring, preferably stirring for 48-52 h, and then carrying out reduced pressure distillation on a reaction product, wherein the vacuum degree of the reduced pressure distillation is preferably 0.061MPa, the distillation temperature of the reduced pressure distillation is preferably 45 ℃, and the reduced pressure distillation is preferably continued until a fraction is not distilled, so as to prepare a mixed product; mixing the mixed product with unsaturated carboxylic acid, and adding deionized water to obtain a solution A;
dissolving allyl trimethyl ammonium chloride, methyl allyl polyoxyethylene ether and methoxy polyethylene glycol-acrylamide (MPEG-ACA) in deionized water, preferably transferring the obtained mixture into a 1000ml round-bottom three-mouth flask together after dissolving the allyl trimethyl ammonium chloride, the methyl allyl polyoxyethylene ether and the methoxy polyethylene glycol-acrylamide (MPEG-ACA) in the deionized water, and then adding an oxidant and unsaturated carboxylic acid into the round-bottom three-mouth flask to serve as reaction base liquid;
step three, mixing a reducing agent, a chain transfer agent and deionized water to obtain a solution B;
step four, heating the reaction base solution to 45-55 ℃ while stirring, then simultaneously dripping the solution A and the solution B, wherein the time for dripping the solution A and the solution B is preferably 2.5-3 h, controlling the temperature to react at 45-55 ℃ after dripping is finished, and the time for reacting at 45-55 ℃ is preferably 2-3 h;
and step five, after the reaction is finished, cooling the solution to 25-30 ℃, adjusting the pH value to 6.0-6.5, preferably adjusting the pH value by using liquid alkali with the mass concentration of 32% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer, wherein after the pH value is adjusted, a step of supplementing water is preferably added, and the water is supplemented until the solid content is 40%.
On the basis of the scheme, further, in the step one, the mixed product prepared by reduced pressure distillation comprises a monomer 1 and a monomer 2;
the structural formula of the monomer 1 is as follows:
the structural formula of the monomer 2 is as follows:
on the basis of the scheme, the invention also provides a preferable scheme of the preparation method, which comprises the following steps:
(1) weighing the raw material components in parts by weight.
(2) Dissolving 2.0-8.0 parts by weight of allyl amine in 100-200 parts by weight of methanol solution, adjusting the temperature to 5-10 ℃, dropwise adding 3.0-20 parts by weight of acrylamide under the protection of nitrogen, electromagnetically stirring for 48-52 h, carrying out reduced pressure distillation on a reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, and carrying out reduced pressure distillation until fractions are not distilled out to obtain a mixture of a monomer 1 and a monomer 2;
the structural formula of the monomer 1 is as follows:
the structural formula of the monomer 2 is as follows:
and mixing the mixture with 10-30 parts by weight of organic carboxylic acid, and adding 30-60 parts by weight of deionized water to obtain solution A.
(3) Dissolving 10-15 parts by weight of allyl trimethyl ammonium chloride, 90-150 parts by weight of methallyl polyoxyethylene ether and 60-100 parts by weight of methoxy polyethylene glycol-acrylamide (MPEG-ACA) in 200-300 parts by weight of deionized water, transferring into a 1000ml round bottom three-neck flask, and adding 1-5 parts by weight of oxidant and the rest 10-30 parts by weight of organic carboxylic acid as reaction base liquid.
(4) 0.5-1.0 part by weight of reducing agent, 1.5-2.5 parts by weight of chain transfer agent and 20-60 parts by weight of deionized water are mixed to obtain solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 45-55 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 2.5-3 h, and carrying out heat preservation reaction for 2-3 h.
(6) After the reaction is finished, cooling the solution to 25-30 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate water reducer.
Compared with the prior art, the ether anti-mud type super-early-strength polycarboxylate superplasticizer and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
1. according to the ether anti-mud type super-early-strength polycarboxylate water reducer, a large number of early-strength groups such as amino groups, amide groups and the like are introduced through the Michael addition reaction of allyl amine and acrylamide, so that the early-strength effect is increased, and the polycarboxylate water reducer with high-density early-strength groups and short side chains is synthesized.
2. The ether anti-mud type super early strength polycarboxylate superplasticizer of the invention introduces methoxy polyethylene glycol-acrylamide (MPEG-ACA) with molecular weight of 3000-.
3. According to the ether anti-mud type super-early-strength polycarboxylate water reducer, allyl trimethyl ammonium chloride is introduced into the polycarboxylate water reducer through free radical copolymerization, and cations contained in the allyl trimethyl ammonium chloride promote the molecules of the polycarboxylate water reducer to have good mud resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following examples and comparative examples:
example 1
(1) Weighing the following raw material components in parts by weight: 120g of methyl allyl polyoxyethylene ether (molecular weight 4000), 80g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 4000), 12g of allyl trimethyl ammonium chloride, 30g of acrylic acid, 9.0g of acrylamide, 4.5g of allylamine, 3.5g of hydrogen peroxide, 1.0g of disodium hydrogen phosphite, 2.1g of mercaptopropionic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 4.5g of allylamine in 150g of methanol solution, adjusting the temperature to 10 ℃, dropwise adding 9.0g of acrylamide under the protection of nitrogen, electromagnetically stirring for 52h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled off, mixing the residual 16g of liquid with 20g of acrylic acid, and adding 40g of deionized water to obtain a solution A.
(3) 12g of allyl trimethyl ammonium chloride, 120g of methyl allyl polyoxyethylene ether and 80g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) are dissolved in 250g of deionized water at 10 ℃, transferred into a 1000ml round-bottom three-neck flask, and added with 3.5g of hydrogen peroxide and the rest 10g of acrylic acid as reaction base liquid.
(4) 1.0g of disodium hydrogenphosphite, 2.1g of mercaptopropionic acid and 40g of deionized water were mixed to prepare a solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 45 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 3.0h, and carrying out heat preservation reaction for 2.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Example 2
(1) Weighing the following raw material components in parts by weight: 90g of methyl allyl polyoxyethylene ether (molecular weight 4000), 60g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 3000), 10g of allyl trimethyl ammonium chloride, 20g of acrylic acid, 3.5g of acrylamide, 2.0g of allyl amine, 1.0g of ammonium persulfate, 0.5g of potassium thiosulfate, 1.5g of mercaptopropionic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 2.0g of allylamine in 100g of methanol solution, adjusting the temperature to 10 ℃, dropwise adding 3.5g of acrylamide under the protection of nitrogen, electromagnetically stirring for 52h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled off, mixing the remaining 9.0g of liquid with 10g of acrylic acid, and adding 40g of deionized water to obtain solution A.
(3) 10g of allyl trimethyl ammonium chloride, 90g of methallyl polyoxyethylene ether and 60g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) were dissolved in 220g of deionized water at 10 ℃, transferred to a 1000ml round-bottom three-neck flask, and 1.0g of ammonium persulfate and the remaining 10g of acrylic acid were added as a reaction base solution.
(4) 0.5g of potassium thiosulfate, 1.5g of mercaptopropionic acid and 20g of deionized water were mixed as solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 50 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 2.5h, and carrying out heat preservation reaction for 3.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Example 3
(1) Weighing the following raw material components in parts by weight: 150g of methyl allyl polyoxyethylene ether (molecular weight 4000), 100g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 5000), 15g of allyl trimethyl ammonium chloride, 40g of methacrylic acid, 12g of acrylamide, 5.0g of allyl amine, 4.0g of ammonium persulfate, 1.0g of ammonium formate, 2.5g of thiomalic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 5.0g of allylamine in 200g of methanol solution, adjusting the temperature to 5 ℃, dropwise adding 12g of acrylamide under the protection of nitrogen, electromagnetically stirring for 48h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled, mixing the residual 23g of liquid with 25g of methacrylic acid, and adding 60g of deionized water to obtain solution A.
(3) 15g of allyl trimethyl ammonium chloride, 150g of methallyl polyoxyethylene ether and 100g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) were dissolved in 300g of deionized water at 15 ℃, transferred to a 1000ml round-bottom three-neck flask, and 4.0g of ammonium persulfate and the remaining 15g of methacrylic acid were added as a reaction base solution.
(4) 1.0g of ammonium formate, 2.5g of thiomalic acid and 30g of deionized water were mixed as solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 50 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 2.5h, and carrying out heat preservation reaction for 2.5 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Example 4
(1) Weighing the following raw material components in parts by weight: 132g of methyl allyl polyoxyethylene ether (molecular weight 4000), 88g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 4500), 14g of allyl trimethyl ammonium chloride, 20g of methacrylic acid, 20g of acrylic acid, 17g of acrylamide, 8.0g of allyl amine, 3.2g of hydrogen peroxide, 0.8g of potassium thiosulfate, 2.3g of thiomalic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 8.0g of allylamine in 150g of methanol solution, adjusting the temperature to 5 ℃, dropwise adding 17g of acrylamide under the protection of nitrogen, electromagnetically stirring for 50h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled, mixing the remaining 30g of liquid with 20g of methacrylic acid, and adding 60g of deionized water to obtain solution A.
(3) 14g of allyltrimethylammonium chloride, 132g of methallylpolyoxyethylene ether and 88g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) were dissolved in 260g of deionized water at 15 ℃ and transferred into a 1000ml round-bottom three-neck flask, and 3.2g of hydrogen peroxide and 20g of acrylic acid were added as a reaction base solution.
(4) 0.8g of potassium thiosulfate, 2.3g of thiomalic acid and 30g of deionized water were mixed to obtain solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 55 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 3.0h, and carrying out heat preservation reaction for 2.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Comparative example 1
(1) Weighing the following raw material components in parts by weight: 120g of methyl allyl polyoxyethylene ether (molecular weight 4000), 80g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 4000), 12g of allyl trimethyl ammonium chloride, 30g of acrylic acid, 3.5g of hydrogen peroxide, 1.0g of disodium hydrogen phosphite, 2.1g of mercaptopropionic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) 20g of acrylic acid was dissolved in 40g of deionized water as solution A.
(3) 12g of allyl trimethyl ammonium chloride, 120g of methyl allyl polyoxyethylene ether and 80g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) are dissolved in 250g of deionized water at 10 ℃, transferred into a 1000ml round-bottom three-neck flask, and added with 3.5g of hydrogen peroxide and the rest 10g of acrylic acid as reaction base liquid.
(4) 1.0g of disodium hydrogenphosphite, 2.1g of mercaptopropionic acid and 40g of deionized water were mixed to prepare a solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 45 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 3.0h, and carrying out heat preservation reaction for 2.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Comparative example 2
(1) Weighing the following raw material components in parts by weight: 90g of methyl allyl polyoxyethylene ether (molecular weight 4000), 10g of allyl trimethyl ammonium chloride, 20g of acrylic acid, 3.5g of acrylamide, 2.0g of allyl amine, 1.0g of ammonium persulfate, 0.5g of potassium thiosulfate, 1.5g of mercaptopropionic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 2.0g of allylamine in 100g of methanol solution, adjusting the temperature to 10 ℃, dropwise adding 3.5g of acrylamide under the protection of nitrogen, electromagnetically stirring for 52h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled off, mixing the remaining 9.0g of liquid with 10g of acrylic acid, and adding 40g of deionized water to obtain solution A.
(3) 10g of allyl trimethyl ammonium chloride and 90g of methyl allyl polyoxyethylene ether are dissolved in 220g of deionized water at 10 ℃, transferred into a 1000ml round bottom three-neck flask, and added with 1.0g of ammonium persulfate and the rest 10g of acrylic acid as reaction base liquid.
(4) 0.5g of potassium thiosulfate, 1.5g of mercaptopropionic acid and 20g of deionized water were mixed as solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 50 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 2.5h, and carrying out heat preservation reaction for 3.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Comparative example 3
(1) Weighing the following raw material components in parts by weight: 150g of methyl allyl polyoxyethylene ether (molecular weight 4000), 100g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 5000), 40g of methacrylic acid, 12g of acrylamide, 5.0g of allylamine, 4.0g of ammonium persulfate, 1.0g of ammonium formate, 2.5g of thiomalic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) Dissolving 5.0g of allylamine in 200g of methanol solution, adjusting the temperature to 5 ℃, dropwise adding 12g of acrylamide under the protection of nitrogen, electromagnetically stirring for 48h, carrying out reduced pressure distillation on the reaction product, keeping the vacuum degree at 0.061MPa and the distillation temperature at 45 ℃, carrying out reduced pressure distillation until fraction is not distilled, mixing the residual 23g of liquid with 25g of methacrylic acid, and adding 60g of deionized water to obtain solution A.
(3) 150g of methyl allyl polyoxyethylene ether and 100g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) were dissolved in 300g of deionized water at 15 ℃, transferred to a 1000ml round-bottom three-neck flask, and 4.0g of ammonium persulfate and the remaining 15g of methacrylic acid were added as a reaction base solution.
(4) 1.0g of ammonium formate, 2.5g of thiomalic acid and 30g of deionized water were mixed as solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 50 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 2.5h, and carrying out heat preservation reaction for 2.5 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Comparative example 4
(1) Weighing the following raw material components in parts by weight: 132g of methyl allyl polyoxyethylene ether (molecular weight 4000), 88g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) (molecular weight 4500), 14g of allyl trimethyl ammonium chloride, 20g of methacrylic acid, 20g of acrylic acid, 17g of acrylamide, 8.0g of allyl amine, 3.2g of hydrogen peroxide, 0.8g of potassium thiosulfate, 2.3g of thiomalic acid, deionized water and a proper amount of liquid alkali with the mass concentration of 32%.
(2) 17g of acrylamide, 8.0g of allylamine and 20g of methacrylic acid were mixed and 60g of deionized water was added as solution A.
(3) 14g of allyltrimethylammonium chloride, 132g of methallylpolyoxyethylene ether and 88g of methoxypolyethylene glycol-acrylamide (MPEG-ACA) were dissolved in 260g of deionized water at 15 ℃ and transferred into a 1000ml round-bottom three-neck flask, and 3.2g of hydrogen peroxide and 20g of acrylic acid were added as a reaction base solution.
(4) 0.8g of potassium thiosulfate, 2.3g of thiomalic acid and 30g of deionized water were mixed to obtain solution B.
(5) Stirring the base solution in the round-bottom three-neck flask, heating to 55 ℃, simultaneously dropwise adding the solution A and the solution B, wherein the dropwise adding time of the solution A and the solution B is 3.0h, and carrying out heat preservation reaction for 2.0 h.
(6) After the reaction is finished, cooling the solution to 25 ℃, adjusting the pH value to 6.0-6.5 by using 32% liquid alkali in mass concentration, and supplementing water until the solid content is 40% to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
Comparative example 5
A commercial early strength polycarboxylate water reducer KH-ZQ1 is adopted.
Comparative example 6
The method adopts a foreign early strength polycarboxylate superplasticizer MasterGlenium ACE 8308.
And (3) carrying out concrete performance comparison and soil resistance tests on the ether anti-mud type super-early-strength polycarboxylate superplasticizer synthesized in the examples 1-4 and the comparative examples 1-4, the comparative example 5 and the comparative example 6, wherein Fujian cement is adopted, and the concrete mixing ratio is as follows: 440kg/m cement3145kg/m of water3669kg/m of sand31188kg/m of stone3The experimental temperature is 25 ℃, the folding and fixing amount of the additive is 0.25 percent of the cementing material, and the obtained results are shown in the table 1:
TABLE 1 comparison of concrete Properties
Measuring the net slurry fluidity according to GB/T8077-2000 'test method for homogeneity of concrete admixture', replacing cement with corresponding mass by montmorillonite with different mass, fixing the water cement ratio to be 0.29, adjusting the mixing amount of the water reducing agent to ensure that the net slurry fluidity is about 280mm when the mixing amount of the montmorillonite is 0, and the result is shown in Table 2:
TABLE 2 soil resistance test
As can be seen from Table 1, the compressive strength values of 1d, 3d, 7d and 28d of the ether anti-mud type super early strength polycarboxylate water reducers prepared in examples 1 to 4 are all obviously higher than those of comparative examples 1 to 6, which shows that the polycarboxylate water reducer prepared by the invention can obviously improve the early strength of concrete. As can be seen from Table 2, when the addition amount of the montmorillonite is 0%, the net slurry fluidity of the comparative examples 1 to 6 is similar to that of the examples 1 to 4, and when the addition amount of the montmorillonite is 0.5% and 1%, the net slurry fluidity of the examples 1 to 4 is obviously higher than that of the comparative examples 1 to 6, which shows that the polycarboxylic acid water reducer prepared by the invention has good soil tolerance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The ether anti-mud type super early strength polycarboxylate superplasticizer is characterized by having the following structural formula:
wherein a is 1 to 33, b is 1 to 555, c is 1 to 140, d is 0 to 140, e is 1 to 110, f is 0 to 37, and m is 65110, n 89, R is H or CH3。
2. The ether anti-mud type super early strength polycarboxylate superplasticizer is characterized by comprising the following preparation raw materials: methyl allyl polyoxyethylene ether, methoxypolyethylene glycol-acrylamide, allyl trimethyl ammonium chloride, unsaturated carboxylic acid, allyl amine, acrylamide, an oxidizing agent, a reducing agent, a chain transfer agent and methanol.
3. The ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2, characterized by comprising the following raw materials for preparation in parts by weight:
4. the ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2 or 3, characterized in that: the molecular weight of the methoxypolyethylene glycol-acrylamide is 3000-5000, and the molecular weight of the methallyl polyoxyethylene ether is 4000.
5. The ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2 or 3, characterized in that: the unsaturated carboxylic acid is one or a mixture of two of acrylic acid and methacrylic acid.
6. The ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2 or 3, characterized in that: the oxidant is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
7. The ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2 or 3, characterized in that: the reducing agent is one or more of disodium hydrogen phosphite, potassium thiosulfate and ammonium formate.
8. The ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 2 or 3, characterized in that: the chain transfer agent is one or two of thiomalic acid and mercaptopropionic acid.
9. The preparation method of the ether anti-mud type super early strength polycarboxylate superplasticizer according to any one of claims 2 to 8, which is characterized by comprising the following preparation steps:
dissolving allyl amine in methanol, adjusting the temperature to 5-10 ℃, dropwise adding acrylamide under a protective atmosphere, stirring, and carrying out reduced pressure distillation on a reaction product to obtain a mixed product; mixing the mixed product with unsaturated carboxylic acid, and adding deionized water to obtain a solution A;
dissolving allyl trimethyl ammonium chloride, methyl allyl polyoxyethylene ether and methoxypolyethylene glycol-acrylamide in deionized water, and adding an oxidant and unsaturated carboxylic acid as reaction base liquid;
step three, mixing a reducing agent, a chain transfer agent and deionized water to obtain a solution B;
step four, heating the reaction base solution to 45-55 ℃ while stirring, then simultaneously dropwise adding the solution A and the solution B, and after dropwise adding is finished, controlling the temperature to be 45-55 ℃ for reaction;
and step five, after the reaction is finished, cooling the solution to 25-30 ℃, and adjusting the pH value to 6.0-6.5 to obtain the ether anti-mud type super early strength polycarboxylate superplasticizer.
10. The method for preparing the ether anti-mud type super early strength polycarboxylate superplasticizer according to claim 9, wherein in the first step, the mixed product obtained by reduced pressure distillation comprises a monomer 1 and a monomer 2;
the structural formula of the monomer 1 is as follows:
the structural formula of the monomer 2 is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911339722.9A CN112708044B (en) | 2019-12-23 | 2019-12-23 | Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911339722.9A CN112708044B (en) | 2019-12-23 | 2019-12-23 | Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112708044A true CN112708044A (en) | 2021-04-27 |
| CN112708044B CN112708044B (en) | 2022-07-05 |
Family
ID=75541110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911339722.9A Active CN112708044B (en) | 2019-12-23 | 2019-12-23 | Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112708044B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898061A (en) * | 2012-10-25 | 2013-01-30 | 山东省建筑科学研究院 | Assistant for polycarboxylic acid water reducing agent and preparation method thereof |
| CN105271900A (en) * | 2015-10-14 | 2016-01-27 | 广东红墙新材料股份有限公司 | Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer |
| CN105330835A (en) * | 2015-11-12 | 2016-02-17 | 黎明职业大学 | Alpha-acrylamido-omega-methoxy polyethylene glycol active macromonomer and preparation method thereof |
| CN107236089A (en) * | 2017-05-27 | 2017-10-10 | 湖南金华达建材有限公司 | A kind of low viscous type polycarboxylate water-reducer and its simple method for preparing |
| CN107265907A (en) * | 2017-07-07 | 2017-10-20 | 江苏中铁奥莱特新材料股份有限公司 | A kind of amphoteric antibacterial polycarboxylic acid series high efficiency water reducing agent and preparation method thereof |
-
2019
- 2019-12-23 CN CN201911339722.9A patent/CN112708044B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898061A (en) * | 2012-10-25 | 2013-01-30 | 山东省建筑科学研究院 | Assistant for polycarboxylic acid water reducing agent and preparation method thereof |
| CN105271900A (en) * | 2015-10-14 | 2016-01-27 | 广东红墙新材料股份有限公司 | Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer |
| CN105330835A (en) * | 2015-11-12 | 2016-02-17 | 黎明职业大学 | Alpha-acrylamido-omega-methoxy polyethylene glycol active macromonomer and preparation method thereof |
| CN107236089A (en) * | 2017-05-27 | 2017-10-10 | 湖南金华达建材有限公司 | A kind of low viscous type polycarboxylate water-reducer and its simple method for preparing |
| CN107265907A (en) * | 2017-07-07 | 2017-10-20 | 江苏中铁奥莱特新材料股份有限公司 | A kind of amphoteric antibacterial polycarboxylic acid series high efficiency water reducing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112708044B (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325234B (en) | Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof | |
| CN109021181A (en) | A kind of poly carboxylic acid series water reducer and preparation method thereof for having both viscosity reduction and protecting function of collapsing | |
| KR100771024B1 (en) | Cement admixture and cement composition | |
| CN112708045B (en) | Low-sensitivity super-early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN110003402A (en) | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability | |
| CN110642993B (en) | Preparation method of retarding ether polycarboxylate superplasticizer | |
| CN107286298B (en) | Slow-release polycarboxylate superplasticizer and preparation method thereof | |
| CN106432628B (en) | A kind of muting sensitive induction reactance mud ether-ether copoly type polycarboxylate water-reducer and preparation method thereof | |
| WO2021103473A1 (en) | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108047396B (en) | Multi-cation mud-resistant polycarboxylate superplasticizer and preparation method thereof | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN108218284B (en) | Concrete water reducing agent composition | |
| CN110845672A (en) | Polycarboxylic acid series concrete gel reducing agent and preparation method thereof | |
| CN111777722A (en) | Anti-mud slump-retaining polycarboxylate superplasticizer and preparation method thereof | |
| CN110734244B (en) | Anti-mud polycarboxylate superplasticizer and preparation method thereof | |
| CN107954627B (en) | Composite concrete retarder and preparation method thereof | |
| CN104945576B (en) | A kind of preparation method of high efficiency water reducing agent, product and application | |
| CN110643003B (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| CN108047390B (en) | Preparation method of anti-mud-reduction type polycarboxylate superplasticizer | |
| CN112708048B (en) | Ester anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN112194762B (en) | Preparation method of non-crosslinked reticular polycarboxylic acid water reducing agent | |
| CN111961148B (en) | Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN112708044B (en) | Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN112708043B (en) | Amine ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN113683736B (en) | Viscosity-reducing polycarboxylate superplasticizer for high-strength concrete and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |